ES2318381T3 - COMPOUNDS CONTAINING UNITS OF 3, 4-METHYLENDIOXY-THIOPHEN. - Google Patents

Abstract

Neutral compounds with optionally substituted 3,4-methylenedioxy-thiophene units are new. Neutral compounds containing n repeating units of formula (I) and optionally m units of formula (II), with end groups R 3> and R 4>, are new. R 1>, R 2>H, optionally substituted 1-20C alkyl (optionally with 1-5 in-chain O and/or S atoms), 1-20C (per)fluoroalkyl, 1-20C alkoxy, optionally substituted 6-24C aryl, alkylaryl or aryloxy, or optionally substituted 2-24C heteroaryl, or R 1> and R 2> together may form an optionally substituted 1-20C alkylene group (optionally with 1-5 in-chain O and/or S as above), 1-20C dioxyalkylene, 6-30C dialkylenearylene or 6-24C dioxyarylene; X 1>optionally substituted vinylidene, arylidene or heteroarylidene; n : 1-1000; m : 0-1000; (m+n) : at least 2; R 3>, R 4>H, 1-20C alkyl, (per)fluoroalkyl or alkoxy, or 6-24C aryl, 1-20C alkylaryl, 1-20C aryloxy or 1-20C heteroaryl (all optionally substituted) . Independent claims are also included for (1) a method for the production of these compounds by metal-organic reaction(s) (2) electronic components containing these compounds . [Image].

Description

Compounds containing units of 3,4-methylenedioxy-thiophene.

The invention relates to compounds containing 3,4-methylenedioxy-thiophene units (units of thieno [3,4-d] -1,3-dioxol)  eventually substituted, to its preparation, as well as to its use as organic semiconductors.

The field of molecular electronics has developed rapidly in the last 15 years with the discovery of conductive and semiconductor organic compounds. In this period of time a large number of compounds were found, which have semiconductor or electro-optical properties. It is a general understanding that molecular electronics will not displace conventional semiconductor component links based on silicon. Instead, it is based on the fact that the molecular electronic component elements will open new sectors of applications, in which the suitability for the coating of large surfaces, structural flexibility, workability at low temperatures and low costs are needed . Currently, semiconductor organic compounds are being developed for application sectors, such as organic field effect transistors (OFET's = O rganische F eld E ffekt T ransistoren), organic luminescent diodes (OLED's, from O rganische L umin e szenz d ioden ), sensors and photovoltaic elements. By means of a simple structuring and integration of the OFET's in integrated organic semiconductor circuits, cheap solutions for smart cards (in English smart cards) or price tags are made possible, which until now cannot be done with the help of silicon technology because of the price and the lack of flexibility of the silicon component links. Also, OFET's could be used as connection elements in flexible matrix advertisements with a large surface area. A compilation of organic semiconductors, integrated semiconductor circuits and their applications is described for example in Electronics 2002, volume 15, page 38.

Known organic semiconductor compounds they are, for example, polyfluorenes and copolymers of fluorenes, such as e.g. poly (9,9-dioctyl-fluorene-co-bitiophene), with which some mobilities of the bearers of electric charges, hereinafter also abbreviated mobilities, up to 0.02 cm2 / Vs (Science 2000, volume 290, page 2123). With a cop (3-hexyl-thiophene-2,5-diyl) regorregular even mobility of up to 0.1 was achieved cm2 / Vs (Science 1998, volume 280, page 1741). Others representatives of semiconductor organic compounds are, by for example, oligothiophenes, particularly those that have alkyl substituents located at the ends, and pentacene. A typical mobilities, eg for α, α'-dihexil-quater-, -quinque- and -sexi-thiophene are located in 0.05-0.1 cm2 / Vs. The compounds described above are restricted however only for use in component parts (opto) -electronics. So, some of these compounds have, for example, phase transformations, which exclude their use above a temperature that is typical for the respective compound, or its mobilities are not enough to some applications.

There have been several attempts to prepare oligomers based on alkylenedioxy thiophene units, in particular based on units of 3,4-ethylenedioxy-thiophene, and Use them as organic semiconductors. It is disadvantageous not Despite the fact that these oligo-alkylenedioxy-thiophenes, about all corresponding compounds of 3,4-ethylenedioxy-thiophene, are very sensitive to oxidation. In this way, your employment as Organic semiconductor is possible only in a restricted way, since an eventual doping of the organic semiconductor would lead to a bad modulation of the electric current. Only in one very recent past were described by Roncali and collaborators, in Journal of Organic Chemistry, 2003, 68, 5357-5360, a synthesis of oligo (3,4-ethylenedioxy-thiophenes),  which have a reduced sensitivity to oxidation. I dont know know so far, however, results for these compounds as regards the suitability for employment as Organic semiconductors in transistors or other parts (opto) electronic components.

There remains, therefore, a need for compounds, which can be used as semiconductors organic

A mission was, therefore, to prepare new organic semiconductor compounds, which have a small sensitivity to oxidation and are well suited for use as organic semiconductors in component parts (opto) electronic.

Surprisingly, it was finally found that neutral compounds, that is to say that they are presented in the form no oxidized, which have units of 3,4-methylenedioxy-thiophene, as successively also called simplified, but with the same meaning, methylenedioxy thiophene units, are stable against oxidation to a large extent and can be used as semiconductors

Compounds of the present invention are compounds neutrals of the general formula (I)

one

in the that

R1 and R2 represent H,

the number of repeated units of the general formula (I) is n, representing

n an integer from 2 to 1,000, so preferred from 2 to 200;

and the compound has extreme groups R 3 and R 4,

representing R 3 and R 4, independently of each other, H or an alkyl group of C 1 -C 20 linear or branched.

In formula I the asterisk (*) characterizes in each case to a binding site for contiguous groups or for groups R 3 or R 4 located at the ends.

In the cases of compounds conforming to invention is about polymers. With the concept of polymers, encompass, within the scope of the invention, all those compounds in which n is an integer greater than 1. In addition, they must understood as polymers all those compounds that are either polydisperses, that is to say they have a weight distribution molecular, or are monodispersed, that is to say they have a molecular weight uniform. Preferably, the compounds according to the invention are monodispersed in the sense of the preceding definition.

R1 and R2 represent, in the formula general (I), H,

R 3 and R 4 represent, in the formula general (I), independently of one another, H or an alkyl group of linear or branched C 1 -C 20, such as eg methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl, iso-butyl, tert-butyl, n-pentyl, 1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 1-ethyl-propyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl.

As an example for compliant compounds to the invention the following must be mentioned:

bis (methylenedioxy thiophene), ter (methylenedioxy thiophene)           quater (methylenedioxy thiophene), quinque (methylenedioxy thiophene), sexi (methylenedioxy thiophene), septi (methylenedioxy thiophene),              octi (methylenedioxy thiophene) and a poly- (methylenedioxy-thiophene). The enumeration serves for the illustrative explanation of the invention and should not be understood as exclusive

Additionally preferred, they are subject to present invention the compounds according to the invention in which R1 and R2 represent H.

By way of example for such compounds according to the invention the following should be mentioned:

2-ethyl-bis (methylenedioxy-thiophene), 2-ethyl-ter- (methylenedioxy-thiophene), 2-ethyl-quater (methylenedioxy-thiophene), 2-ethyl-quinque (methylenedioxy-thiophene), 2-ethyl-sexi (methylenedioxy-thiophene), 2-ethyl-septi (methylenedioxy-thiophene), 2-ethyl-octi (methylenedioxy-thiophene), 2-propyl-bis (methylenedioxy-thiophene), 2-propyl-ter (methylenedioxy-thiophene), 2-propyl-quater (methylenedioxy-thiophene), 2-propyl-quinque (methylenedioxy-thiophene), 2-propyl-sexi- (methylenedioxy-thiophene), 2-propyl-septi (methylenedioxy-thiophene), 2-propyl-octi (methylenedioxy-thiophene), 2-butyl-bis (methylenedioxy-thiophene), 2-butyl-ter (methylenedioxy-thiophene), 2-butyl-quater (methylenedioxy-thiophene), 2-butyl-quinque (methylenedioxy-thiophene), 2-butyl-sexi (methylenedioxy-thiophene), 2-butyl-septi (methylenedioxy-thiophene), 2-butyl-octi (methylenedioxy-thiophene), 2-pentyl-bis (methylenedioxy-thiophene), 2-pentyl-ter ( methylenedioxy-thiophene), 2-pentyl-quater (methylenedioxy-thiophene), 2-pentyl-quinque- (methylenedioxy-thiophene), 2-pentyl-sexi (methylenedioxy-thiophene), 2-pentyl-septi (methylenedioxy-thiophene), 2 P entyl-octi (methylenedioxy-thiophene), 2-hexyl-bis (methylenedioxy-thiophene), 2-hexyl-ter (methylenedioxy-thiophene), 2-hexyl-quater (methylenedioxy-thiophene), 2-hexyl-quinque- (methylenedioxy) -thiophene), 2-hexyl-sexi (methylenedioxy-thiophene), 2-hexyl-septi (methylenedioxy-thiophene), 2-hexyl-octi (methylenedioxy-thiophene), 2,5'-diethyl-bis (methylenedioxy-thiophene) , 2,5'-dipropyl-bis (methylenedioxy-thiophene), 2,5'-dibutyl-bis (methylenedioxy-thiophene), 2,5'-dipentyl-bis (methylenedioxy-thiophene), 2,5'-dihexyl- bis (methylenedioxy-thiophene), 2,5'-dioctyl-bis (methylenedioxy-thiophene), 2,5 '' - dimethyl-ter (methylenedioxy-thiophene), 2,5 '' - diethyl-te- (methylenedioxy-thiophene) ), 2,5 '' - dipropyl-ter (methylenedioxy-thiophene), 2,5 '' - dibutyl-ter (methylenedioxy-thiophene), 2,5 '' - dihexyl-ter (methylenedioxy-thiophene), 2.5 '' -dioctyl-ter- (methylenedioxy-thiophene), 2,5 '' - didecyl-ter (methylenedioxy-thiophene), 2,5 '' - didodecyl-ter (methylenedioxy-thiophene), 2.5 '' - dimethyl quater (methylenedioxy thiophene),
2,5 '''- diethyl-quater (methylenedioxy-thiophene), 2,5''' - dihexyl-quater (methylenedioxy-thiophene), 2,5 '''- didecyl-quater (methylenedioxy-thiophene), 2, 5 '''' - diethyl-quinque (methylenedioxy-thiophene), 2,5 '''' - dihexyl-quinque (methylenedioxy-thiophene), 2,5 '''' - didecyl
quinque (methylenedioxy-thiophene), 2,5 '''''- dimethyl-sexi (methylenedioxy-thiophene), 2,5''''' - diethyl-sexi (methylenedioxy-thiophene),
2,5 '''''- dihexil-sexi (methylenedioxy-thiophene). The enumeration serves for the illustrative explanation of the invention and is not to be understood as exclusive.

Additionally preferred, they are subject to present invention those compounds according to the invention, in the which R 3 and R 4 represent H.

In other preferred embodiments, the Compounds according to the invention are those of the general formula (II)

2

in which R 1 and R 2 they represent H, and R 3, R 4 and n have the meanings previously indicated for the general formula (I). They are valid in a similar way certain preferred intervals and combinations of these intervals preferred.

In other preferred embodiments, the Compounds according to the invention are those of the general formula (II-a)

3

in which R 1, R 2, R 3 and R 4 represent H, and n has the meanings above indicated for the general formula (I). They are valid in a way analogous certain intervals preferred.

By way of example for such compounds of the general formula (II-a) according to the invention have been to mention the following:

bis (methylenedioxy thiophene), ter (methylenedioxy thiophene),            quater (methylenedioxy thiophene), quinque (methylenedioxy thiophene), sexi (methylenedioxy thiophene), septi- (methylenedioxy thiophene),      octi (methylenedioxy thiophene), novi (methylenedioxy thiophene), deci (methylenedioxy thiophene), undeci (methylenedioxy thiophene),          dodeci (methylenedioxy thiophene), and a poly (methylenedioxy thiophene). Enumeration it serves for the illustrative explanation of the invention and must not understood as exclusive.

In principle it is possible to prepare the compounds according to the invention by different procedures, which are known primarily to an expert in the specialty based on at least one organometallic reaction.

It is the subject of the invention, therefore, a procedure for the preparation of a compound according to invention, the compound according to the invention being prepared by at least one organometallic reaction.

A procedure is preferred in this context, wherein the compound according to the invention is prepared by a Kumada link, Suzuki link or link from Stille.

In a preferred embodiment variant, the compounds according to the invention are prepared by a variant of the Suzuki coupling, often also called Suzuki condensation. The condensation of Suzuki or respectively Suzuki coupling, that is the halide reaction of aryl and aryl boronic acid compounds with a compound of Pd as a catalyst in the presence of a base, has been described eg in the quotation of Suzuki et al., Chem. Rev. 1995, 95, 2457-2483. In a preferred form of embodiment, the process according to the invention is carried out, according to a variant according to the invention of this Suzuki coupling, reacting organyl halides or respectively acid esters organyl boronals eventually in the presence of a base and / or of at least one catalyst, which contains a metal of the subgroup VIII of the periodic system of the elements, named in the following briefly metal of subgroup VIII.

The preferred embodiment of the procedure according to the invention (Suzuki coupling) is carried carried out at a temperature of + 20 ° C to + 200 ° C, preferably of + 40 ° C to + 150 ° C, especially preferably from + 80 ° C to + 130 ° C, within an organic solvent or a mixture of such solvents

As catalysts, which contain a metal of subgroup VIII, all compounds come into question in principle appropriate containing a metal of subgroup VIII, so preferably Pd, Ni or Pt, especially preferably Pd. The o the catalyst (s) is preferably used in proportions of 0.05% by weight to 10% by weight, so especially preferred from 0.5% by weight to 5% by weight, based on total weight of the compounds to be coupled.

Especially suitable catalysts are complex compounds of metals of subgroup VIII, in particular complex compounds of palladium (0), which are stable in the presence of air, complex compounds of Pd, which can be easily reduced with organometallic reagents (e.g. lithium and alkyl compounds or organic magnesium compounds), or phosphines to give complex compounds of palladium (0), or complex compounds of palladium (2), possibly with the addition of PPh3 or other phosphines. For example, PdCl 2 (PPh 3) 2, PdBr 2 can be used
(PPh 3) 2 or Pd (OAc) 2 or mixtures of these compounds with the addition of PPh 3. Preferably, Pd (PPh3) 4 is used without or with the addition of phosphines, and in a preferred embodiment without the addition of phosphines, which is available in a cheap form. As phosphines, PPh 3, PEtPh 2, PMePh 2, PEt 2 Ph or PEt 3 are preferably used, particularly preferably PPh 3.

However, it is also possible to use as catalysts certain palladium compounds without the addition of phosphines,  such as for example Pd (OAc) 2.

Hydroxides, such as, for example, NaOH, KOH, LiOH, Ba (OH) 2, can be used as bases,
Ca (OH) 2, alkoxides, such as eg NaOEt, KOEt, LiOEt, NaOMe, KOMe, LiOMe, alkali metal salts of carboxylic acids, such as eg carbonate, hydrogen carbonate, acetate , citrate, acetyl-acetonate or sodium, potassium or lithium glycinate, or other carbonates, such as eg Cs2CO3 or Tl2CO3, phosphates, such as e.g. Sodium phosphate, potassium phosphate or lithium phosphate, or mixtures of these compounds. Preferably, sodium carbonate is used. The bases can be used as solutions in water or as suspensions in organic solvents, such as toluene, dioxane or DMF (dimethyl formamide). Water solutions are preferred, since the products obtained, because of their small water solubility, can thus be easily separated from the reaction mixture.

It is also possible to use as agents adjuvants other salts, such as for example LiCl or LiBr.

How organic solvents come into question fundamentally all solvents, or all mixtures of solvents, which do not react with boronic acid esters. These are as a rule some compounds that have no halogen atom or any hydrogen atom that is reactive against boronic acid esters. Appropriate solvents are, for example, alkanes such as pentane, hexane and heptane, aromatic compounds such as benzene, toluene and xylenes, compounds containing groups of ethers such as dioxane, dimethoxyethane and tetrahydrofuran, and polar solvents such as                dimethyl formamide or dimethyl sulfoxide. Preferably, in the process according to the invention aromatic compounds are used as solvents Toluene is very especially preferred. It is also possible to use mixtures of two or more of solvents as solvents. these solvents.

The organyl halides, used in this procedure, can be prepared according to procedures known or can be purchased commercially. The preparation of boronic acid esters can be carried out for example by the reaction of aryl halides and of a bis (organil) -diborane by means of a metal catalyzed coupling (application document International Patent WO-A-01/29051 A1 Tetrahedron Lett. 2002, page 5649), through a coupling of halides of oligothiophenes with, for example, pinacol-borano (J. Org. Chem. 1997, volume 62, page 6458; J. Organomet. Chem. 2001, volume 640, page 197; Chem. Commun. 2002, page 1566) or by a reaction of compounds organometallic, eg organic magnesium compounds (e.g. Grignard compounds), or organic lithium compounds, with boronic acid esters. These procedures are known. for an expert in the specialty.

In another preferred embodiment additionally, the compounds according to the invention are prepared by a coupling of Kumada. The coupling of Kumada, that is the reaction of an aryl halide and a compound of aril-Grignard in the presence of a Pd catalyst or Ni, as described in the quotation of Kumada et al., J. Am. Chem. Soc., 1972, 94, 4373-4376. In a way preferred embodiment, the process according to the invention is carries out, according to a variant according to the invention of this Kumada coupling, reacting halides of aryl or respectively of heteroaryl and Grignard compounds of aryl halides or heteroaryl respectively in the presence of a catalyst, which contains a metal of subgroup VIII of the system newspaper of the elements, hereinafter referred to briefly metal of subgroup VIII. The preferred embodiment of the procedure according to the invention (Kumada coupling) is carried carried out at a temperature of 0 ° C to 200 ° C, preferably + 20 ° C to + 150 ° C, especially preferably from + 40 ° C to + 130 ° C, within an organic solvent or a mixture of such  solvents

As catalysts, which contain a metal of subgroup VIII, all compounds come into question in principle appropriate, containing a metal of subgroup VIII, so preferably Pd or Ni, especially preferably Pd. He or the catalyst (s) is preferably used in proportions of 0.05% by weight to 10% by weight, so especially preferred from 0.5% to 5% by weight, based on weight total of the compounds to be coupled.

Especially suitable catalysts are certain complex compounds of metals of subgroup VIII, in particular complex compounds of palladium (0), which are stable in the presence of air, complex compounds of Pd, which can easily reduce with organometallic reagents (e.g. lithium and alkyl compounds or organic magnesium compounds) or with phosphines to give complex compounds of palladium (0), or complex compounds of palladium (2) eventually with addition of PPh3 or other phosphines. For example, you can employ PdCl 2 (PPh 3) 2, PdBr 2 (PPh 3) 2 or Pd (OAc) 2, or mixtures of these compounds, with addition of diphenyl phosphine ethane (dppe) or diphenyl-phosphino-propane (dppp) or 1,1'-bis (diphenyl phosphino) ferrocene  (dppf). They are preferably used as catalysts PdCl2 (dppe), PdCl2 (dppp) and PdCl_ {2} (dppf).

How organic solvents come into question fundamentally all solvents, or all mixtures of solvents, which do not react with Grignard reagents. These they are as a rule some compounds that have no atom of halogen or any hydrogen atom that is reactive against Grignard compounds. Appropriate solvents are, for example, aromatic compounds such as benzene, toluene and xylenes, compounds containing groups of ethers such as dioxane, dimethoxyethane, diethyl ether, dibutyl ether and tetrahydrofuran. From In a preferred manner, the process according to the invention is used solvents of the type of ethers. It is very especially preferred tetrahydrofuran. It is also possible to use solvents as mixtures of two or more of these solvents.

In another preferred embodiment additionally, the compounds according to the invention are prepared by a Stille link. The Stille coupling, that is the reaction of an aryl halide and an aryl compound alkenyl stannyl in the presence of a catalyst of Pd, eg described in the quote by Stille et al., Angew. Chem. 1986, 98, 504. In a preferred embodiment, the procedure according to the invention is carried out in accordance with a preferred variant of this Stille coupling, making react aryl halides or heteroaryl respectively and aryl- and alkenyl-stanyl compounds in presence of a catalyst, which contains a metal of subgroup VIII of the periodic system of the elements, hereinafter referred to as briefly metal of subgroup VIII. The preferred form of carrying out the process according to the invention (coupling of Stille) is carried out at a temperature of 0ºC to 200ºC, so preferably from + 20 ° C to + 150 ° C, especially preferably from + 40 ° C to + 130 ° C, within an organic solvent or a mixture of such solvents.

As catalysts, which contain a metal of subgroup VIII, all appropriate compounds, which contain a metal of subgroup VIII, in particular Pd. He or the catalysts
dor (s) is preferably used in proportions of 0.05% by weight to 10% by weight, especially preferably from 0.5% by weight to 5% by weight, based on the total weight of the compounds to be coupled.

Especially suitable catalysts are complex compounds of metals of subgroup VIII, in particular complex compounds of palladium (0), which are stable in the presence of air, complex compounds of Pd, which can be easily reduced with organometallic reagents (eg compounds of lithium and alkyl or organic compounds of magnesium) or with phosphines to give complex compounds of palladium (0), or complex compounds of palladium (2), optionally with the addition of PPh3 or other phosphines. For example, PdCl2 (PPh3) 2, PdBr2 (PPh3) 2 can be used
or Pd (OAc) 2 or mixtures of these compounds with the addition of PPh3. Preferably, Pd (PPh3) 4 is used without or with the addition of phosphines, in a preferred embodiment without the addition of phosphines, which is available in a cheap form. As phosphines, PPh 3, PEtPh 2, PMePh 2, PEt 2 Ph or PEt 3 are preferably used, particularly preferably PPh 3.

However, it is also possible to use as catalysts palladium compounds without the addition of phosphines, such as for example Pd (OAc) 2.

How organic solvents come into question fundamentally all solvents, or all mixtures of solvents, which do not react with stanyl compounds. These are as a rule some compounds, which have no halogen atom or hydrogen atoms that are reactive against stanyl compounds. Appropriate solvents are, for example, aromatic compounds such as benzene, toluene and xylenes, compounds containing groups of ethers such as dioxane, dimethoxyethane, diethyl ether, dibutyl ether and tetrahydrofuran, or polar solvents such as dimethyl formamide, N-methyl-pyrrolidone or acetonitrile. It is also possible to use as mixtures certain mixtures of two or more of these solvents.

The treatment of the respective mixture of reaction is carried out according to known procedures, e.g. by dilution, precipitation, filtration, extraction, washing, recrystallization from organic solvents, chromatography and / or sublimation. For example, a treatment can be carried out in such a way that the reaction mixture, after having completed the reaction, it is poured into a mixture of water (ice) of an acidic nature, eg prepared from acid 1 molar hydrochloric, and toluene, the organic phase is separated, washed With water, the product contained as solid material is separated by filtration, washed with toluene and then dried under vacuum. The compounds according to the invention can already be obtained without subsequent additional purification processes, in a quality and high purity. However, it is possible to purify additionally these products according to procedures known, eg by recrystallization, chromatography or sublimation.

The compounds according to the invention are electrically neutral and semiconductors and present a small sensitivity to oxidation. In addition, they can be applied well from a solution. As a consequence, they are appropriate good for use as organic semiconductors in parts (opto) electronic components.

This is surprising, because the original monomer compound, 3,4-methylenedioxy-thiophene or respectively thieno [3,4-d] -1,3-dioxol, is known to an expert in the specialty from a series of publications, and he had to assume that the compounds with methylenedioxy thiophene units behave in a analogously to other compounds that contain units of                           3,4-alkylenedioxy thiophene. By consequently, it was expected that the compounds containing methylenedioxy thiophene units have a state stable electrically charged or respectively oxidized and that the Neutral state is rather unstable. Thus, eg by Ahonen and collaborators, Synthetic Metals (1997), 84 (1-3), 215-216 are described certain polymers of methylenedioxy thiophene only in an oxidized form, that is to say cationic, that by consequently they cannot be used as semiconductors, but as organic conductors (compare the application document for European patent EP-A-339,340). Some non-oxidized compounds, that is neutral, with units of                 3,4-Methylenedioxy-thiophene have not been described so far in the bibliography.

In addition, it is the subject of the present invention, therefore both, the use of the compounds according to the invention and organic semiconductors in electronic component elements, in active electronic component elements and light emitters, such as field effect transistors, luminescent diodes organic, photovoltaic cells, lasers or sensors.

For this, the compounds according to the invention they are applied as layers on appropriate substrates, by example on silicon wafers, polymer sheets or moons of glass, which are provided with electrical structures or Electronic For the application come into consideration in principle all application procedures that are known for an expert in the specialty. For example, the compounds of the general formula (I) can be applied from one phase gas or from a solution, the solvent being evaporated then. The application from a solution can be carry out in accordance with known procedures, for example by atomization, immersion, printing and scratching, coating by centrifugation (in English spin coating) and by jet printing of ink (Ink-Jet). Compounds conforming to invention can also be applied from a gas phase, eg by application from a vapor phase. In this way you can get some layers with the smallest defects and the most high mobility of electric charges.

It is the subject of the present invention therefore, in addition, an electronic component element that contains less a compound according to the invention.

The following Examples are for the illustrative explanation and demonstration of the invention, but not They constitute no limitation.

Examples Example 1 Synthesis of bis (methylenedioxy thiophene) (II-a-1) (bis-MDT)

4

3.96 g of 3,4-Methylenedioxy-thiophene se dissolved under an atmosphere of N2 in 100 ml of Tetrahydrofuran (THF) absolutized (abs.) and cooled to 0 ° C. To solution cooled to 0 ° C is added dropwise 20 ml of a 1.6 M solution of n-butyllithium in n-hexane The mixture is stirred at 0 ° C for 30 min. After this, 4.41 g of CuCl2 are added at once and the The mixture is then stirred for 12 h at 23 ° C. After having poured into a mixture of ice and water filtered with suction 1.9 g (= 48% of theoretical yield) of bis (3,4-methylenedioxy-thiophene) (II-a-1).

Mp .: 225-231 ° C

Elementary Analysis:

measured: C: 46.7% H: 2.25% S: 24.6% calculated: C: 47.0% H: 2.37% S: 25.6% (for C10H6 O4 S2)

1 H-NMR spectrum (CDCl 3; ppm δ vs. TMS): 6.00 (2H), 6.28 (4H)

       \ vskip1.000000 \ baselineskip
    

Example 2 Synthesis of 2-hexyl bis (methylenedioxy thiophene) (II-1)

5

To 20 ml of anhydrous THF are added at -20 ° C 3.52 ml of a 2.5 M solution of N-butyllithium in hexane. Mix stir for 1 h and then add 2.03 g of bis-MDT (II-1), prepared according with Example 1, in 50 ml of THF. The mixture is stirred at -20 ° C. for an additional hour and then added at -20 1.65 g hexyl bromide. The reaction mixture is thawed and hydrolyzes with water. The aqueous phase is extracted three times, each time with 50 ml of methylene chloride, and the solvent is removed totally from the organic phases gathered. 0.7 g of 2-hexyl-bis- (methylenedioxy-thiophene), after chromatography in the presence of silica gel, in Shape of a light gray solid material.

Example 3 Synthesis of 2,5 '' '- dihexil-quater- (methylenedioxy-thiophene) (II-2)

6

In 20 ml of THF it is previously available at -70ºC 1 ml of a 1.6 M solution of n-butyllithium in n-hexane Then they are added drop by drop 0.157 ml of diisopropyl amine and the mixture is stirred for 1 h. Subsequently, 0.5 g of 2-hexyl-bis- (methylenedioxy-thiophene) - prepared according to Example 2 -. The mixture is thawed at -20 ° C and stir for 1 h. After this it cools again to -78 ° C and about 0.16 g of chloride are added thereto anhydrous copper (II). The mixture is stirred for 1 h at -70 ° C and then defrost at 23 ° C. Then it hydrolyzes with water, the aqueous phase is extracted three times, each time with 50 ml of methylene chloride, and the solvent is completely removed from the organic phases gathered. 0.24 g of 2,5 '' '- dihexil-quater (methylenedioxy-thiophene) (II-2) as a brown powder yellowish.

Claims (7)

1. Neutral compound of the general formula (I) 7 in the that R1 and R2 represent H; the number of repeated units of the general formula (I) is n, representing n an integer from 2 to 1,000, and the compound carries R3 end groups and R 4, representing R 3 and R 4, independently of each other, H or an alkyl group of C 1 -C 20 linear or branched. 2. Compound according to claim 1, characterized in that R3 and R4 represent H. 3. Process for the preparation of a compound according to claim 1 or 2, characterized in that the compound is prepared by at least one organometallic reaction. 4. Method according to claim 3, characterized in that the compound is prepared by a Kumada coupling, a Suzuki coupling or a Stille coupling. 5. Use of the compounds according to claim 1 or 2 as organic semiconductors in elements Electronic components. 6. Use according to claim 5, characterized in that the electronic component elements are chosen from the set consisting of: field effect transistors, light emitting component elements such as organic luminescent diodes, photovoltaic cells, lasers and sensors. 7. Electronic component element, characterized in that it contains at least one compound according to claim 1 or 2.